The discovery of stable and noble-metal-free catalysts toward efficient electrochemical reduction of nitrogen (N ) to ammonia (NH ) is highly desired and significantly critical for the earth nitrogen cycle. Here, based on the theoretical predictions, MoS is first utilized to catalyze the N reduction reaction (NRR) under room temperature and atmospheric pressure. Electrochemical tests reveal that such catalyst achieves a high Faradaic efficiency (1.17%) and NH yield (8.08 × 10 mol s cm ) at -0.5 V versus reversible hydrogen electrode in 0.1 m Na SO . Even in acidic conditions, where strong hydrogen evolution reaction occurs, MoS is still active for the NRR. This work represents an important addition to the growing family of transition-metal-based catalysts with advanced performance in NRR.
The industrial artificial fixation of atmospheric N2 to NH3 is carried out using the Haber–Bosch process that is not only energy‐intensive but emits large amounts of greenhouse gas. Electrochemical reduction offers an environmentally benign and sustainable alternative for NH3 synthesis. Although Mo‐dependent nitrogenases and molecular complexes effectively catalyze the N2 fixation at ambient conditions, the development of a Mo‐based nanocatalyst for highly performance electrochemical N2 fixation still remains a key challenge. Here, greatly boosted electrocatalytic N2 reduction to NH3 with excellent selectivity by defect‐rich MoS2 nanoflowers is reported. In 0.1 m Na2SO4, this catalyst attains a high Faradic efficiency of 8.34% and a high NH3 yield of 29.28 µg h−1 mg−1cat. at −0.40 V versus reversible hydrogen electrode, much larger than those of defect‐free counterpart (2.18% and 13.41 µg h−1 mg−1cat.), with strong electrochemical stability. Density functional theory calculations show that the potential determining step has a lower energy barrier (0.60 eV) for defect‐rich catalyst than that of defect‐free one (0.68 eV).
Heteratom
doping is a possible way to tune the hydrogen evolution
reaction (HER) catalytic capability of electrocatalysts. In this work,
we report the development of Mn-doped CoP (Mn–Co–P)
nanosheets array on Ti mesh (Mn–Co–P/Ti) as an efficient
3D HER electrocatalyst with good stability at all pH values. Electrochemical
tests demonstrate that Mn doping leads to enhanced catalytic activity
of CoP. In 0.5 M H2SO4, this Mn–Co–P/Ti
catalyst drives 10 mA cm–2 at an overpotential of
49 mV, which is 32 mV less than that for CoP/Ti. To achieve the same
current density, it demands overpotentials of 76 and 86 mV in 1.0
M KOH and phosphate-buffered saline, respectively. The enhanced HER
activity for Mn–Co–P can be attributed to its more thermo-neutral
hydrogen adsorption free energy than CoP, which is supported by density
functional theory calculations.
As a non‐toxic species, Zn fulfills a multitude of biological roles, but its promoting effect on electrocatalysis has been rarely explored. Herein, the theoretic predications and experimental investigations that nonelectroactive Zn behaves as an effective promoter for CoP‐catalyzed hydrogen evolution reaction (HER) in both acidic and alkaline media is reported. Density function theory calculations reveal that Zn doing leads to more thermal‐neutral hydrogen adsorption free energy and thus enhanced HER activity for CoP catalyst. Electrochemical tests show that a Zn0.08Co0.92P nanowall array on titanium mesh (Zn0.08Co0.92P/TM) needs overpotentials of only 39 and 67 mV to drive a geometrical catalytic current of 10 mA cm‐2 in 0.5 m H2SO4 and 1.0 m KOH, respectively. This Zn0.08Co0.92P/TM is also superior in activity over CoP/TM for urea oxidation reaction (UOR), driving 115 mA cm‐2 at 0.6 V in 1.0 m KOH with 0.5 m urea. The high HER and UOR activity of this bifunctional electrode enables a Zn0.08Co0.92P/TM‐based two‐electrode electrolyzer for energy‐saving hydrogen production, offering 10 mA cm‐2 at a low voltage of 1.38 V with strong long‐term electrochemical stability.
The topotactic conversion of cobalt phosphide nanoarray on Ti mesh into a cobalt phosphate nanoarray (Co-Pi NA) via oxidative polarization in phosphate-buffered water is presented. As a 3D oxygen evolution reaction (OER) catalyst electrode at neutral pH, the resulting Co-Pi NA/Ti shows exceptionally high catalytic activity and demands an overpotential of only 450 mV to drive a geometrical catalytic current density of 10 mA cm . Notably, this catalyst also shows superior long-term electrochemical stability. The excellent catalytic activity can be attributed to that such 3D nanoarray configuration allows for the exposure of more active sites and the easier diffusion of electrolytes and oxygen.
The synthesis of
NH3 is mainly dominated by the traditional
energy-consuming Haber–Bosch process with a mass of CO2 emission. Electrochemical conversion of N2 to
NH3 emerges as a carbon-free process for the sustainable
artificial N2 reduction reaction (NRR), but requires an
efficient and stable electrocatalyst. Here, we report that the Mo2C nanorod serves as an excellent NRR electrocatalyst for artificial
N2 fixation to NH3 with strong durability and
acceptable selectivity under ambient conditions. Such a catalyst shows
a high Faradaic efficiency of 8.13% and NH3 yield of 95.1
μg h–1 mg–1cat at −0.3 V in 0.1 M HCl, surpassing the majority of reported
electrochemical conversion NRR catalysts. Density functional theory
calculation was carried out to gain further insight into the catalytic
mechanism involved.
Electrohydrogenation
of N2 to NH3 is emerging
as an environmentally benign strategy to tackle the issues associated
with the energy-intensive, CO2-emitting Haber–Bosch
process. However, the method is severely challenged by N2 activation and needs efficient N2 reduction reaction
(NRR) catalysts. Here, we report that multishelled hollow Cr2O3 microspheres (MHCMs), which are synthesized by a facile
synthetic route, can serve as efficient and selective non-noble metal
electrocatalysts for NRR. In 0.1 M Na2SO4 solution,
the MHCMs achieve a high Faradaic efficiency (6.78%) and a large NH3 yield (25.3 μg h–1 mgcat
–1) at −0.9 V vs reversible hydrogen electrode.
The MHCMs also exhibit high stability during the reaction. Density
functional theory calculations suggest that NRR over MHCMs occurs
via both distal associative and partially alternative routes.
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